Salts of lewis acid/acid adducts and catalyst activators therefrom

ABSTRACT

A compound useful as a cocatalyst or cocatalyst component, especially for use as an addition polymerization catalyst compound, corresponding to the formula: (A*hu +a) b (Z*J* j ) −c   d , wherein: 
     A* is a proton or a cation of from 1 to 80 atoms, preferably 1 to 60 atoms, not counting hydrogen atoms, said A* having a charge +a; 
     Z* is an anion group of from 1 to 50 atoms, preferably 1 to 30 atoms, not counting hydrogen atoms, further containing two or more Lewis base sites, said Z* being the conjugate base of an inorganic Bronsted acid or a carbonyl- or non-cyclic, imino-group containing organic Bronsted acid; 
     J* independently each occurrence is a Lewis acid of from 1 to 80 atoms, preferably 1 to 60 atoms, not counting hydrogen atoms, coordinated to at least one Lewis base site of Z*, and optionally two or more such J* groups may be joined together in a moiety having multiple Lewis acidic functionality; 
     j is a number from 1 to 12; and 
     a, b, c, and d are integers from 1 to 3, with the proviso that a×b is equal to c×d.

CROSS REFERENCE STATEMENT

This application claims the benefit of U.S. Provisional Application No.60/307,249, filed Jul. 23, 2001.

BACKGROUND INFORMATION

The present invention relates to compounds that are useful as catalystcomponents. More particularly the present invention relates to suchcompounds that are particularly adapted for use in the coordinationpolymerization of unsaturated compounds comprising an anion containingat least two Lewis basic sites derived from certain inorganic or organicBronsted acids, which are coordinated to Lewis acids. Such compounds areparticularly advantageous for use in forming supported polymerizationcatalysts wherein at least the catalyst activator is chemically attachedto a substrate material.

It is previously known in the art to activate Ziegler-Nattapolymerization catalysts, particularly such catalysts comprising Group3-10 metal complexes containing delocalized π-bonded ligand groups, bythe use of Bronsted acid salts capable of transferring a proton to forma cationic derivative or other catalytically active derivative of suchGroup 3-10 metal complex. Preferred Bronsted acid salts are suchcompounds containing a cation/anion pair that is capable of renderingthe Group 3-10 metal complex catalytically active. Suitable activatorscomprise fluorinated arylborate anions, such astetrakis(pentafluorophenyl)borate. Additional suitable anions includesterically shielded diboron anions of the formula:

wherein:

S is hydrogen, alkyl, fluoroalkyl, aryl, or fluoroaryl, Ar^(F) isfluoroaryl, and X¹ is either hydrogen or halide, disclosed in U.S. Pat.No. 5,447,895. Additional examples include carborane compounds such asare disclosed and claimed in U.S. Pat. No. 5,407,884.

Examples of preferred charge separated (cation/anion pair) activatorsare ammonium, sulfonium, or phosphonium salts capable of transferring ahydrogen ion, disclosed in U.S. Pat. Nos. 5,198,401, 5,132,380,5,470,927 and 5,153,157, as well as oxidizing salts such as ferrocenium,silver or lead salts, disclosed in U.S. Pat. Nos. 5,189,192 and5,321,106 and strongly Lewis acidic salts such as carbonium or silyliumsalts, disclosed in U.S. Pat. Nos. 5,350,723 and 5,625,087.

Further suitable activators for the above metal complexes include strongLewis acids including tris(perfluorophenyl)borane andtris(perfluorobiphenyl)borane. The former composition has beenpreviously disclosed for the above stated end use in EP-A-520,732,whereas the latter composition is similarly disclosed by Marks, et al.,in J. Am. Chem. Soc., 118, 12451-12452 (1996).

In WO99/42467, WO01/23442 and WO02/08303 expanded ionic catalystactivators are disclosed that are well suited for use as olefinpolymerization activators.

Despite the satisfactory performance of the foregoing catalystactivators under a variety of polymerization conditions, there is stilla need for improved cocatalysts for use in the activation of variousmetal complexes especially under a variety of reaction conditions.Accordingly, it would be desirable if there were provided compounds thatcould be employed in solution, slurry, gas phase or high pressurepolymerizations and under homogeneous or heterogeneous processconditions having improved activation properties.

SUMMARY OF THE INVENTION

According to the present invention there are now provided compoundsuseful as catalyst activators corresponding to the formula:(A*^(+a))_(b)(Z*^(J)*_(j))^(−c) _(d), wherein:

A* is a proton or a cation of from 1 to 80 atoms, preferably 1 to 60atoms, not counting hydrogen atoms, said A* having a charge +a,

Z* is an anion group of from 1 to 50 atoms, preferably 1 to 30 atoms,not counting hydrogen atoms, further containing two or more Lewis basesites, said Z* being the conjugate base of an inorganic Bronsted acid ora carbonyl- or non-cyclic, imino-group containing organic Bronsted acid;

J* independently each occurrence is a Lewis acid of from 1 to 80 atoms,preferably 1 to 60 atoms, not counting hydrogen atoms, coordinated to atleast one Lewis base site of Z*, and optionally two or more such J*groups may be joined together in a moiety having multiple Lewis acidicfunctionality;

j is a number from 1 to 12; and

a, b, c, and d are integers from 1 to 3, with the proviso that a×b isequal to c×d.

The foregoing compounds may be utilized in combination with one or moreGroup 3-10 or Lanthanide metal complexes to form catalyst compositionsfor polymerization of addition polymerizable monomers, especiallyethylenically unsaturated monomers, most preferably, C_(2-20,000)α-olefins. Additionally, the compounds may be utilized to form latentactivators, that is, compounds that may themselves not cause a metalcomplex to become catalytically active due, for example, to the presenceof a reactive group such as a hydroxyl group, but which may be convertedto an active compound by, for example, in-situ reaction of the hydroxylgroup with a Lewis acid, especially an aluminum hydrocarbyl compound, oran alkali metal halide or ammonium halide salt. Moreover, such compoundsmay be deposited onto solid supports, such as by impregnation, surfacedeposition, physisorption or chemical reaction with the support,reactive functionality of the support, or chemical modifiers associatedwith the support, to form heterogeneous catalyst components for use inpreparing heterogeneous catalyst compositions for use in polymerizationof the foregoing monomers.

Thus, in one embodiment of the invention, the foregoing compoundscontaining hydroxyl or other reactive functionality are used to formsupported catalyst components by reaction of the hydroxyl group thereofwith reactive functionality of a support material, or by conversion ofthe dialkylaluminumoxyhydrocarbyl, trihydrocarbylsiloxyhydrocarbyl orhydrocarbyloxyhydrocarbyl group to a reactive functionality and reactionthereof with reactive functionality of a support material. The resultingsupported catalyst components are highly resistant to loss of activatorcompound in a liquid reaction medium such as occurs in a slurrypolymerization. One or more Group 3-10 or Lanthanide metal complexes,preferably a Group 4 metal complex, and additional additives, modifiersand adjuvants may be added to the catalyst component, either before,after or simultaneous with addition of the cocatalyst of the presentinvention, to form the fully formulated catalyst composition.Accordingly, in one embodiment of the invention the foregoing structurescan be created on a surface containing chemically or physically bondedanionic groups, Z*.

Another embodiment of the invention is a composition of mattercomprising the admixture or reaction product, optionally in an inertdiluent, of an inorganic Bronsted acid or a carbonyl- or non-cyclic,imino-group-containing organic Bronsted acid; from one to twelve molesper mole of Bronsted acid of a Lewis acid having from 1 to 80,preferably 1 to 60 atoms, not counting hydrogen atoms; optionally aLewis base of from 1 to 80, preferably 1 to 60 atoms, not countinghydrogen, preferably an amine or phosphine containing Lewis base; andfurther optionally an organoaluminum compound, preferably an alumoxane,especially methylalumoxane or modified methylalumoxane.

Additionally according to the present invention there is provided acatalyst composition for polymerization of an ethylenically unsaturated,polymerizable monomer comprising, in combination, the above describedactivator compound or composition of matter, a Group 3-10 metal complexthat is capable of activation to form an addition polymerizationcatalyst, or the reaction product of such combination, and optionally asupport.

Additionally according to the present invention there is provided aprocess for polymerization of one or more ethylenically unsaturated,polymerizable monomers comprising contacting the same, optionally in thepresence of an inert aliphatic, alicyclic or aromatic hydrocarbon, withthe above catalyst compositions or supported catalyst compositions.

The foregoing compounds are uniquely adapted for use in activation of avariety of metal complexes, especially Group 4 metal complexes, understandard and a typical olefin polymerization conditions. Because of thisfact, the foregoing compounds are capable of forming highly desirableolefin polymers in high efficiency. Especially desirably, the compoundsare readily hydrolyzed and are easily removed from the polymer productafter polymerization.

DETAILED DESCRIPTION OF THE INVENTION

All references herein to elements belonging to a certain Group refer tothe Periodic Table of the Elements published and copyrighted by CRCPress, Inc., 1999. Also any reference to the Group or Groups shall be tothe Group or Groups as reflected in this Periodic Table of the Elementsusing the IUPAC system for numbering groups. For purposes of UnitedStates patent practice, the contents of any patent, patent applicationor publication referenced herein are hereby incorporated by reference intheir entirety herein, especially with respect to the disclosure ofstructures, synthetic techniques and general knowledge in the art. Theterm “comprising” and derivatives thereof, when used herein with respectto a composition, mixture, or sequence of steps, is not intended toexclude the additional presence of any other compound, component orevent.

The catalyst activators of the invention are further characterized inthe following manner. A*^(+a) is desirably chosen to provide overallneutrality to the compound and to not interfere with subsequentcatalytic activity. Moreover, the cation may participate in theformation of the active catalyst species, desirably through a protontransfer, oxidation, or ligand abstraction mechanism, or a combinationthereof. Additionally, certain cations beneficially improve thesolubility of the resulting activator in particular reaction media underuse conditions. For example, in the homopolymerization orcopolymerization of aliphatic olefins, particularly in the solutionphase, an aliphatic diluent is commonly used. Accordingly, cationicspecies that are relatively soluble in such reaction media, or renderthe catalyst activator more soluble therein are highly preferred.

Examples of suitable cations include: ammonium, sulfonium, phosphonium,oxonium, carbonium, and silylium cations, preferably those containing upto 80 atoms not counting hydrogen, a proton, as well as ferrocenium,Ag⁺, Pb⁺², or similar oxidizing cations. In a preferred embodiment, a,b, c and d are all equal to one.

Preferred A*^(+a) cations are protons, and ammonium cations, especiallytrihydrocarbyl-substituted ammonium cations. Examples includetrimethylammonium-, triethylammonium-, tripropylammonium-,tri(n-butyl)ammonium-, methyldi(C₁₄₋₁₈ alkyl)ammonium-, dimethyl(C₁₄₋₁₈alkyl)ammonium-, N,N-dimethylanilinium-, N,N-diethylanilinium-,N,N-dimethyl(2,4,6-trimethylanilinium)-, N,N-di(tetradecyl)lanilinium-,N,N-di(tetradecyl)-2,4,6-trimethylanilinium)-,N,N-di(octadecyl)lanilinium-,N,N-di(octadecyl)-2,4,6-trimethylanilinium)-, andmethyldicyclohexylammonium-cations.

More preferred cations include those containing one or two C₁₀-C₄₀ alkylgroups, such as methylbis(octadecyl)ammonium-,dimethyloctadecylammonium-, methylbis(tetradecyl)ammonium-,bis(octadecyl)anilinium-, andbis(octadecyl)-3,5-dimethylanilinium-cations. It is further understoodthat the cation may comprise a mixture of hydrocarbyl groups ofdiffering lengths. For example, the protonated ammonium cation derivedfrom the commercially available long chain amine comprising a mixture oftwo C₁₄, C₁₆ or C₁₈ alkyl groups and one methyl group. Such amines areavailable from Witco Corp., under the trade name Kemamine™ T9701, andfrom Akzo-Nobel under the trade name Armeen™ M2HT.

Preferably Z* is the conjugate base of an inorganic acid and is selectedfrom the group consisting of: NO₃ ⁻, PO₄ ^(3−,)SO₄ ²⁻, RSO₃ ⁻ and CO₃²⁻, or Z* is the conjugate base of an organic acid and is selected fromthe group consisting of: [RC(O)O]⁻, [RC(NR)NR]⁻, [R′C(O)CRC(O)R′]⁻,[(R′C(O))₃C]⁻, [RC(NR)CRC(NR)R]⁻, and [(RC(NR))₃C]⁻,

wherein each R is independently a hydrogen-; hydrocarbyl-; orhalocarbyl-group; a hydrocarbyl group further substituted with one ormore carbonyl-, halo-, hydroxy-, dialkylamino-, dialkylaluminumoxy-,trihydrocarbylsilyl-, trihydrocarbylsiloxy-, or hydrocarbyloxy-groups;or a halocarbyl group further substituted with one or more carbonyl-,hydroxy-, dialkylamino-, dialkylaluminumoxy-, trihydrocarbylsilyl-,trihydrocarbylsiloxy-, or hydrocarbyloxy-groups; and each R′ isindependently R or two R′ groups may be joined together thereby forminga divalent group.

More preferably, Z* is an acetylacetonate, cyclohexa-1,3-dionate,[RC(O)O]⁻ or NO₃ ⁻, wherein R is a C₆₋₂₄ hydrocarbyl group, mostpreferably a C₁₂₋₂₄ alkyl group, or the conjugate base anion derivedfrom indane-1,3-dione or methyltriacetyl corresponding to the followingstructure:

Coordinated to some or all of the Lewis base sites of the Z* anion, thatis, to the oxygen or nitrogen atoms, are from 1 to 12 Lewis acids, J*,two or more of which may be joined together in a moiety having multipleLewis acidic functionality. Each J* group or when two or more J* groupsare joined together, the resulting combination, is a neutral compound.Optionally, said J* group may comprise a hydroxyl group or a polar groupcontaining quiescent reactive functionality, so long as suchfunctionality does not interfere with the Lewis acid functionalitythereof. Preferably, from 2 to 4 J* groups having from 3 to 100 atomsnot counting hydrogen are present in each compound of the invention.

More specific examples of the foregoing Lewis acid compounds, J*,correspond to the formula:

wherein:

M* is aluminum, gallium or boron;

R¹ and R² independently each occurrence are hydride, halide, or ahydrocarbyl, halocarbyl, halohydrocarbyl, dialkylamido, alkoxide, oraryloxide group of up to 20 carbons, optionally substituted with ahydroxyl group or a polar group containing quiescent reactivefunctionality, and

Ar^(f1)-Ar^(f2) in combination, independently each occurrence, is adivalent fluoro-substituted aromatic group of from 6 to 20 carbons,optionally substituted with a hydroxyl group or a polar group containingquiescent reactive functionality.

Highly preferred Lewis acids are aluminum or boron compoundscorresponding to the formula: AlR¹ ₃, or BR¹ ₃, wherein R¹ independentlyeach occurrence is selected from hydrocarbyl, halocarbyl, andhalohydrocarbyl radicals, or such groups further substituted with ahydroxyl group or a polar group containing quiescent reactivefunctionality, said R¹ having up to 20 carbons. In a more highlypreferred embodiment, R¹ is a C₆₋₂₀ aryl group or a fluorinated C₁₋₂₀hydrocarbyl group, most preferably, a fluorinated aryl group,especially, pentafluorophenyl.

Preferred examples of the foregoing Lewis acid groups containingmultiple Lewis acid sites are:

By the term “polar group containing quiescent reactive functionality” ismeant an oxygen, nitrogen, sulfur, or phosphorus containing ligand groupthat is capped or protected and thereby rendered relatively inert toreaction conditions used in the synthesis or use of the presentcompounds, but wherein the capping or protecting groups may be laterremoved, if desired, thereby generating a reactive polar functionalgroup, especially a hydroxyl group or metallated derivative thereof.Suitable reactive polar functional groups include hydroxyl, thiol,amine, and phosphine groups, or hydrocarbyl-, alkali metal- or Bronstedacid salt-derivatives thereof. Suitable quiescent reactive functionalityincludes the trihydrocarbyllsilyl-, trihydrocarbylgermyl-,dihydrocarbylaluminum-, hydrocarbylzinc- orhydrocarbylmagnesium-functionalized derivative of the foregoing polargroups. Particularly preferred polar containing quiescent reactivefunctional groups are trihydrocarbylsiloxy,trihydrocarbylsiloxy-substituted hydrocarbyl, dihydrocarbylaluminoxy anddihydrocarbylaluminoxy substituted hydrocarbyl groups. Especiallypreferred are the trialkylsiloxy- or dialkylaluminoxy-derivatives ofsuch polar functional groups, containing from 1 to 6 carbon in eachalkyl group. Especially preferred quiescent reactive functional groupsare trimethylsiloxy-groups and diethylaluminoxy-groups.

Such polar group containing quiescent reactive functionality isactivated by reaction with a metal hydrocarbyl-, metal halocarbyl-,hydrocarbylmetaloxy- or metal halohydrodarbyl-compound under ligandexchange conditions, thereby producing a neutral hydrocarbon,halohydrocarbon, trimethylsilylhydrocarbon,trimethylsilylhalo-hydrocarbon or trimethylsilylhalocarbon compound as aby-product. The hydroxyl group or polar group containing quiescentreactive functionality may also be employed to react with hydroxyl-,alkylmetal-, hydrocarbylsilyl-, or hydrocarbylsiloxy-functionality of asolid, particulated, support material, optionally after conversion to ametallated or protonated intermediate. This results in tethering orchemically attaching the activator to the surface of the solid,particulated, support material. The resulting substance demonstratesenhanced resistance to loss or removal when exposed to liquids in apolymerization process.

In a preferred embodiment, the foregoing hydroxyl group or polar groupcontaining quiescent reactive functionality is located in the Z* ligand.Examples include hydroxyl, trialkylsiloxy-, trialkylsiloxyalkyl-,trialkylsiloxyaryl-, and dialkylaluminoxyaryl-substituted derivatives ofcarboxylic acids.

Especially suitable compounds according to the present invention includethe tris(pentafluorophenyl)borane-coordinated derivatives of ammonium-,phosphonium-, sulfonium-, oxonium-, carbonium-, silylium-, lead (II)-,silver- or ferrocenium-carboxylates, acetylacetonates,cyclohexa-1,3-dionates or nitrates. Preferred compounds are the ammoniumsalts, especially those which comprise trihydrocarbyl-substitutedammonium cations, especially trimethylammonium-, triethylammonium-,tripropylammonium-, tri(n-butyl)ammonium-, methyldi(octadecyl)ammonium-,methyldi(tetradecyl)ammonium-, methyl(tetradecyl)(octadecyl)ammonium-,N,N-dimethylanilinium-, N,N-diethylanilinium-,N,N-dimethyl(2,4,6-trimethylanilinium)-, N,N-di(tetradecyl)lanilinium-,N,N-di(tetradecyl)-2,4,6-trimethylanilinium)-,N,N-di(octadecyl)lanilinium-,N,N-di(octadecyl)-2,4,6-trimethylanilinium)-, andmethyldicyclohexylammonium-cations, or mixtures thereof.

Most preferred ammonium cation containing salts are those containingtrihydrocarbyl-substituted ammonium cations containing one or twoC₁₀-C₄₀ alkyl groups, especially methylbis(octadecyl)ammonium- andmethylbis(tetradecyl)ammonium-cations. It is further understood that thecation may comprise a mixture of hydrocarbyl groups of differinglengths. For example, the protonated ammonium cation derived from thecommercially available long chain amine comprising a mixture of two C₁₄,C₁₆ or C₁₈ alkyl groups and one methyl group. Such amines are availablefrom Witco Corp., under the trade name Kemamine™ T9701, and fromAkzo-Nobel under the trade name Armeen™ M2HT.

Most preferred cocatalysts according to the present invention are themono- and bis(tris(pentafluorophenyl)borane)-coordinated derivatives oftrihydrocarbylammonium stearates, 1,3-cylcohexadionates oracetylacetonates, most especiallybis(tris(pentafluorophenyl)borane)-coordinated derivatives ofmethyldioctyldecylammonium stearate, methylditetradecylammoniumstearate, or mixtures thereof, and thebis(tris(pentafluorophenyl)borane)-coordinated derivatives of a reactionproduct formed by contacting of a trihydrocarbylamine with1,3-cylcohexadione or acetylacetone, or mixtures thereof, such as thebis(tris(pentafluorophenyl)borane)-coordinated derivatives of a reactionproduct formed by contacting methyldioctyldecylamine,methylditetradecylamine, or a mixture thereof with 1,3-cylcohexadione,acetylacetone, or a mixture thereof.

The compounds may be prepared by simply combining the Lewis acid, J*, orits Lewis base adduct, such as an ethereate, with the neutral compoundcorresponding to the cation/anion complex, (A*^(+a))_(b)(Z*)^(−c) _(d),or the reaction mixture resulting from contacting a Lewis base, such asan amine, with the Bronsted acid HZ*. They may also be prepared bycombination in any order of the Lewis acid, J*, or its Lewis baseadduct, such as an etherate, with the protonated version of theconjugated base of the Bronsted acid, HZ*, and optionally a Lewis base,such as an amine, derived from A*^(+a). Additionally, they may beprepared by a condensation reaction between a metal salt of the anion,Z*, and a Lewis acid, J*, preferably under phase transfer conditions,using for example a crown ether to solubilize the metal salt ifnecessary, followed by a metathesis reaction with the correspondinghalide salt of the cation, A*^(+a). Addition of the free basecorresponding to the cation, A*^(+a), results in formation of the chargeseparated species, which may be recovered from the reaction mixture bydevolatilization or used without further purification. Finally, they mayalso be prepared by reaction of a metal salt, especially a silver saltof the anion, Z* with the corresponding halide salt of the cation,A*^(+a). Addition of the neutral Lewis acid, J, results in formation ofthe desired product.

If a hydroxyl group or quiescent reactive functionality is present inthe compounds of the present invention, or reactive derivatives thereof,they may be readily attached to a reactive substrate, such as aparticulated solid containing reactive hydrocarbyl groups, especiallyhydrocarbylmetal- or hydrocarbylmetalloid-functionality. Examplesinclude alumina, silica, aluminosilicates, and aluminum magnesiumsilicate materials, containing reactive hydroxyl- orhydrocarbyl-functionality, and such materials treated with any substanceto impart reactive metal-hydrocarbyl or metalloid-hydrocarbylfunctionality. Examples of such treating substances includetrihydrocarbyl aluminum compounds, chlorosilane compounds, and mono- ordi-hydrocarbylsilane compounds that react with a portion or all ofreactive surface hydroxyl functionality of the substrate to form a“capped” derivative. This technique is known in the art and disclosedfor example in U.S. Pat. No. 6,087,293.

Suitable catalysts for use in combination with the foregoing cocatalystsinclude any compound or complex of a metal of Groups 3-10 of thePeriodic Table of the Elements capable of being activated to polymerizeethylenically unsaturated compounds by the present activators. Examplesinclude Group 10 diimine derivatives corresponding to the formula:

wherein

M* is Ni(II) or Pd(II);

K′ is halo, hydrocarbyl, or hydrocarbyloxy;

and the two nitrogen atoms are linked by a bridging system.

Such catalysts have been previously disclosed in J. Am. Chem. Soc., 118,267-268 (1996), J. Am. Chem. Soc., 117,6414-6415 (1995), andOrganometallics, 16, 1514-1516, (1997).

Additional catalysts include derivatives of Group 3, 4, or Lanthanidemetals which are in the +2, +3, or +4 formal oxidation state. Preferredcompounds include metal complexes containing from 1 to 3 π-bondedanionic or neutral ligand groups, which may be cyclic or non-cyclicdelocalized π-bonded anionic ligand groups. Exemplary of such π-bondedanionic ligand groups are conjugated or nonconjugated, cyclic ornon-cyclic dienyl groups, allyl groups, boratabenzene groups, phosphole,and arene groups. By the term “π-bonded” is meant that the ligand groupis bonded to the transition metal by a sharing of electrons from apartially delocalized π-bond.

Each atom in the delocalized π-bonded group may independently besubstituted with a radical selected from the group consisting ofhydrogen, halogen, hydrocarbyl, halohydrocarbyl, hydrocarbyl-substitutedmetalloid radicals wherein the metalloid is selected from Group 14 ofthe Periodic Table of the Elements, and such hydrocarbyl- orhydrocarbyl-substituted metalloid radicals further substituted with aGroup 15 or 16 hetero atom containing moiety. Included within the term“hydrocarbyl” are C₁₋₂₀ straight, branched and cyclic alkyl radicals,C₆₋₂₀ aromatic radicals, C₇₋₂₀ alkyl-substituted aromatic radicals, andC₇₋₂₀ aryl-substituted alkyl radicals. In addition two or more suchradicals may together form a fused ring system, including partially orfully hydrogenated fused ring systems, or they may form a metallocyclewith the metal. Suitable hydrocarbyl-substituted organometalloidradicals include mono-, di- and tri-substituted organometalloid radicalsof Group 14 elements wherein each of the hydrocarbyl groups containsfrom 1 to 20 carbon atoms. Examples of suitable hydrocarbyl-substitutedorganometalloid radicals include trimethylsilyl, triethylsilyl,ethyldimethylsilyl, methyldiethylsilyl, triphenylgermyl, andtrimethylgermyl groups. Examples of Group 15 or 16 hetero atomcontaining moieties include amine, phosphine, ether or thioethermoieties or divalent derivatives thereof, e.g. amide, phosphide, etheror thioether groups bonded to the transition metal or Lanthanide metal,and bonded to the hydrocarbyl group or to the hydrocarbyl-substitutedmetalloid containing group.

Examples of suitable anionic, delocalized π-bonded groups includecyclopentadienyl, indenyl, fluorenyl, tetrahydroindenyl,tetrahydrofluorenyl, octahydrofluorenyl, pentadienyl, cyclohexadienyl,dihydroanthracenyl, hexahydroanthracenyl, decahydroanthracenyl groups,phosphole, and boratabenzene groups, as well ashydrocarbyl-silyl-(including mono-, di-, or tri(hydrocarbyl)silyl)substituted derivatives thereof. Preferred anionic, delocalizedit-bonded groups are cyclopentadienyl, pentamethylcyclopentadienyl,tetramethylcyclopentadienyl,tetramethyl(trimethylsilyl)-cyclopentadienyl, indenyl,2,3-dimethylindenyl, fluorenyl, 2-methylindenyl,2-methyl-4-phenylindenyl, tetrahydrofluorenyl, octahydrofluorenyl, andtetrahydroindenyl.

The boratabenzenes are anionic ligands that are boron containinganalogues to benzene. They are previously known in the art having beendescribed by G. Herberich, et al., in Organometallics, 14,1, 471-480(1995). Preferred boratabenzenes correspond to the formula:

wherein R″ is selected from the group consisting of hydrocarbyl, silyl,N,N-dihydrocarbylamino, or germyl, said R″ having up to 20 non-hydrogenatoms. In complexes involving divalent derivatives of such delocalizedπ-bonded groups one atom thereof is bonded by means of a covalent bondor a covalently bonded divalent group to another atom of the complexthereby forming a bridged system.

Phospholes are anionic ligands that are phosphorus containing analoguesto a cyclopentadienyl group. They are previously known in the art havingbeen described by WO 98/50392, and elsewhere. Preferred phospholeligands correspond to the formula:

wherein R″ is selected from the group consisting of hydrocarbyl, silyl,N,N-dihydrocarbylamino, or germyl, said R″ having up to 20 non-hydrogenatoms, and optionally one or more R″ groups may be bonded togetherforming a multicyclic fused ring system, or form a bridging groupconnected to the metal. In complexes involving divalent derivatives ofsuch delocalized π-bonded groups one atom thereof is bonded by means ofa covalent bond or a covalently bonded divalent group to another atom ofthe complex thereby forming a bridged system.

Phosphinimine/cyclopentadienyl complexes are disclosed in EP-A-890581and correspond to the formula [R***)₃—P═N]_(b)M**(Cp)(L¹)_(3-b),wherein:

R*** is a monovalent ligand, illustrated by hydrogen, halogen, orhydrocarbyl, or two R*** groups together form a divalent ligand,

M** is a Group 4 metal,

Cp is cyclopentadienyl, or similar delocalized π-bonded group,

L¹ is a monovalent ligand group, illustrated by hydrogen, halogen orhydrocarbyl,

b is a number from 1 to 3; and

n is 1 or 2.

A suitable class of catalysts are transition metal complexescorresponding to the formula:

Lp_(l)MX_(m)X′_(n)X″_(p), or a dimer thereof

wherein:

Lp is an anionic, delocalized, π-bonded group that is bound to M,containing up to 50 non-hydrogen atoms, optionally two Lp groups may bejoined together forming a bridged structure, and further optionally oneLp may be bound to X;

M is a metal of Group 4 of the Periodic Table of the Elements in the +2,+3 or +4 formal oxidation state;

X is an optional, divalent group of up to 50 non-hydrogen atoms thattogether with Lp forms a metallocycle with M;

X′ is an optional neutral ligand having up to 20 non-hydrogen atoms;

X″ each occurrence is a monovalent, anionic moiety having up to 40non-hydrogen atoms, optionally, two X″ groups may be covalently boundtogether forming a divalent dianionic moiety having both valences boundto M, or, optionally 2 X″ groups may be covalently bound together toform a neutral, conjugated or nonconjugated diene that is π-bonded to M(whereupon M is in the +2 oxidation state), or further optionally one ormore X″ and one or more X′ groups may be bonded together thereby forminga moiety that is both covalently bound to M and coordinated thereto bymeans of Lewis base functionality;

l is 0, 1 or 2;

m is 0 or 1;

n is a number from 0 to 3;

p is an integer from 0 to 3; and

the sum, 1+m+p, is equal to the formal oxidation state of M, except when2 X″ groups together form a neutral conjugated or non-conjugated dienethat is π-bonded to M, in which case the sum l+m is equal to the formaloxidation state of M.

Preferred complexes include those containing either one or two Lpgroups. The latter complexes include those containing a bridging grouplinking the two Lp groups. Preferred bridging groups are thosecorresponding to the formula (ER*₂)_(x), B(NR**₂), or B(NR**₂)₂, whereinE is silicon, germanium, tin, or carbon, R* independently eachoccurrence is hydrogen or a group selected from silyl, hydrocarbyl,hydrocarbyloxy, and combinations thereof, said R* having up to 30 carbonor silicon atoms, R** independently each occurrence is a group selectedfrom silyl, hydrocarbyl, and combinations thereof, said R** having up to30 carbon or silicon atoms, and x is 1 to 8. Preferably, R*independently each occurrence is methyl, ethyl, propyl, benzyl, butyl,phenyl, methoxy, ethoxy, or phenoxy, and R** is methyl, ethyl, propyl,benzyl or butyl.

Examples of the complexes containing two Lp groups are compoundscorresponding to the formula:

wherein:

M is titanium, zirconium or hafnium, preferably zirconium or hafnium, inthe +2 or +4 formal oxidation state;

R³ in each occurrence independently is selected from the groupconsisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halo andcombinations thereof, said R³ having up to 20 non-hydrogen atoms, oradjacent R³ groups together form a divalent derivative (that is, ahydrocarbadiyl, siladiyl or germadiyl group) thereby forming a fusedring system, and

X″ independently each occurrence is an anionic ligand group of up to 40non-hydrogen atoms, or two X″ groups together form a divalent anionicligand group of up to 40 non-hydrogen atoms or together are a conjugateddiene having from 4 to 30 non-hydrogen atoms forming a π-complex with M,whereupon M is in the +2 formal oxidation state, and

R*, R**, E and x are as previously defined, preferably (ER*₂)_(x) isdimethylsilandiyl or ethylene, and BNR**₂ isdi(isopropyl)aminoborandiyl.

The foregoing metal complexes are especially suited for the preparationof polymers having stereoregular molecular structure. In such capacityit is preferred that the complex possesses C_(s) symmetry or possesses achiral, stereorigid structure. Examples of the first type are compoundspossessing different delocalized π-bonded systems, such as onecyclopentadienyl group and one fluorenyl group. Similar systems based onTi(IV) or Zr(IV) were disclosed for preparation of syndiotactic olefinpolymers in Ewen, et al., J. Am. Chem. Soc. 110, 6255-6256 (1980).Examples of chiral structures include rac bis-indenyl complexes. Similarsystems based on Ti(IV) or Zr(IV) were disclosed for preparation ofisotactic olefin polymers in Wild et al., J. Organomet. Chem., 232,233-47, (1982).

Exemplary bridged ligands containing two π-bonded groups are:dimethylbis(cyclopentadienyl)silane,dimethylbis(tetramethylcyclopentadienyl)silane,dimethylbis(2-ethylcyclopentadien-1-yl)silane,dimethylbis(2-t-butylcyclopentadien-1-yl)silane,2,2-bis(tetramethylcyclopentadienyl)propane,dimethylbis(inden-1-yl)silane, dimethylbis(tetrahydroinden-1-yl)silane,dimethylbis(fluoren-1-yl)silane,dimethylbis(tetrahydrofluoren-1-yl)silane,dimethylbis(2-methyl-4-phenylinden-1-yl)-silane,dimethylbis(2-methylinden-1-yl)silane,di(isopropyl)aminobis(cyclopentadien-1-yl)borandiyl,di(isopropyl)aminobis(2-methyl4-phenylinden-1-yl)-borandiyl,di(isopropyl)aminobis(2-methylinden-1-yl)borandiyl,dimethyl(cyclopentadienyl)(fluoren-1-yl)silane,dimethyl(cyclopentadienyl)(octahydrofluoren-1-yl)silane,dimethyl(cyclopentadienyl)(tetrahydrofluoren-1-yl)silane,(1,1,2,2-tetramethy)-1,2-bis(cyclopentadienyl)disilane,(1,2-bis(cyclopentadienyl)ethane, anddimethyl(cyclopentadienyl)-1-(fluoren-1-yl)methane.

Preferred X″ groups are selected from hydride, hydrocarbyl, silyl,germyl, halohydrocarbyl, halosilyl, silylhydrocarbyl andaminohydrocarbyl groups, or two X″ groups together form a divalentderivative of a conjugated diene or else together they form a neutral,π-bonded, conjugated diene. Most preferred X″ groups are C₁₋₂₀hydrocarbyl groups.

Complexes containing two Lp groups including bridged complexes suitablefor use in the present invention include:

bis(cyclopentadienyl)zirconiumdimethyl,

bis(cyclopentadienyl)zirconium dibenzyl,

bis(cyclopentadienyl)zirconium methyl benzyl,

bis(cyclopentadienyl)zirconium methyl phenyl,

bis(cyclopentadienyl)zirconiumdiphenyl,

bis(cyclopentadienyl)titanium-allyl,

bis(cyclopentadienyl)zirconiummethylmethoxide,bis(cyclopentadienyl)zirconiummethylchloride,

bis(pentamethylcyclopentadienyl)zirconiumdimethyl,

bis(pentamethylcyclopentadienyl)titaniumdimethyl,

bis(indenyl)zirconiumdimethyl,

indenylfluorenylzirconiumdimethyl,

bis(indenyl)zirconiummethyl(2-(dimethylamino)benzyl),

bis(indenyl)zirconiummethyltrimethylsilyl,

bis(tetrahydroindenyl)zirconiummethyltrimethylsilyl,

bis(pentamethylcyclopentadienyl)zirconiummethylbenzyl,

bis(pentamethylcyclopentadienyl)zirconiumdibenzyl,

bis(pentamethylcyclopentadienyl)zirconiummethylmethoxide,

bis(pentamethylcyclopentadienyl)zirconiummethylchloride,

bis(methylethylcyclopentadienyl)zirconiumdimethyl,

bis(butylcyclopentadienyl)zirconiumdibenzyl,

bis(t-butylcyclopentadienyl)zirconiumdimethyl,

bis(ethyltetramethylcyclopentadienyl)zirconiumdimethyl,

bis(methylpropylcyclopentadienyl)zirconiumdibenzyl,

bis(trimethylsilylcyclopentadienyl)zirconiumdibenzyl,

dimethylsilyl-bis(cyclopentadienyl)zirconiumdimethyl,

dimethylsilyl-bis(tetramethylcyclopentadienyl)titanium (III) allyl

dimethylsilyl-bis(t-butylcyclopentadienyl)zirconiumdibenzyl,

dimethylsilyl-bis(n-butylcyclopentadienyl)zirconium bis(trimethylsilyl),

(methylene-bis(tetramethylcyclopentadienyl)titanium(III)2-(dimethylamino)benzyl,

(methylene-bis(n-butylcyclopentadienyl)titanium(III)2-(dimethylamino)benzyl,

dimethylsilyl-bis(indenyl)zirconiumbenzylchloride,

dimethylsilyl-bis(2-methylindenyl)zirconiumdimethyl,

dimethylsilyl-bis(2-methyl-4-phenylindenyl)zirconiumdimethyl,

dimethylsilyl-bis(2-methylindenyl)zirconium-1,4-diphenyl-1,3-butadiene,

dimethylsilyl-bis(2-methyl-4-phenylindenyl)zirconium(II)1,4-diphenyl-1,3-butadiene,

dimethylsilyl-bis(tetrahydroindenyl)zirconium(II)1,4-diphenyl-1,3-butadiene,

di(isopropylamino)borandiylbis(2-methyl-4-phenylindenyl)zirconiumdimethyl,

dimethylsilyl-bis(tetrahydrofluorenyl)zirconium bis(trimethylsilyl),

(isopropylidene)(cyclopentadienyl)(fluorenyl)zirconiumdibenzyl, and

dimethylsilyl(tetramethylcyclopentadienyl)(fluorenyl)zirconium dimethyl.

A further class of metal complexes utilized in the present inventioncorresponds to the preceding formula Lp_(pl)MX_(m)X′_(n)X″_(p), or adimer thereof, wherein X is a divalent group of up to 50 non-hydrogenatoms that together with Lp forms a metallocycle with M.

Preferred divalent X groups include groups containing up to 30non-hydrogen atoms comprising at least one atom that is oxygen, sulfur,boron or a member of Group 14 of the Periodic Table of the Elementsdirectly attached to the delocalized π-bonded group, and a differentatom, selected from the group consisting of nitrogen, phosphorus, oxygenor sulfur that is covalently bonded to M.

A preferred class of such Group 4 metal coordination complexes usedaccording to the present invention corresponds to the formula:

wherein,

M is titanium or zirconium, preferably titanium in the +2, +3, or +4formal oxidation state;

R³ in each occurrence independently is selected from the groupconsisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halo andcombinations thereof, said R³ having up to 20 non-hydrogen atoms, oradjacent R³ groups together form a divalent derivative (that is, ahydrocarbadiyl, siladiyl or germadiyl group) thereby forming a fusedring system,

each X″ is a halo, hydrocarbyl, hydrocarbyloxy or silyl group, saidgroup having up to 20 non-hydrogen atoms, or two X″ groups together forma neutral C₅₋₃₀ conjugated diene or a divalent derivative thereof;

Y is —O—, —S—, —NR*-, —PR*-; and

Z is SiR*₂, CR*₂, SiR*₂SiR*₂, CR*₂CR*₂, CR*=CR*, CR*₂SiR*₂, GeR*₂, orB(NR**₂) wherein R* and R** are as previously defined.

Illustrative Group 4 metal complexes of the latter formula that may beemployed in the practice of the present invention include:

cyclopentadienyltitaniumtrimethyl,

indenyltitaniumtrimethyl,

octahydrofluorenyltitaniumtrimethyl,

tetrahydroindenyltitaniumtrimethyl,

tetrahydrofluorenyltitaniumtrimethyl,

(tert-butylamido)(1,1-dimethyl-2,3,4,9,10-η-1,4,5,6,7,8-hexahydronaphthalenyl)dimethylsilanetitaniumdimethyl,

(tert-butylamido)(1,1,2,3-tetramethyl-2,3,4,9,10-η-1,4,5,6,7,8-hexahydronaphthalenyl)dimethylsilanetitaniumdim

(tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilanetitaniumdibenzyl,

(tert-butylamido)(tetramethyld-η⁵-cyclopentadienyl)dimethylsilanetitaniumdimethyl,

(tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)-1,2-ethanediyltitaniumdimethyl,

(tert-butylamido)(tetramethyl-η⁵-indenyl)dimethylsilanetitaniumdimethyl,

(tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilanetitanium (III) 2-(dimethylamino)benzyl;

(tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilanetitanium(III)allyl,

(tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilanetitanium(III) 2,4-dimethylpentadienyl,

(tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilanetitanium(II) 1,4-diphenyl-1,3-butadiene,

(tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilanetitanium(II) 1,3-pentadiene,

(tert-butylamido)(2-methylindenyl)dimethylsilanetitanium(II)1,4-diphenyl-1,3-butadiene,

(tert-butylamido)(2-methylindenyl)dimethylsilanetitanium(II)2,4-hexadiene,

(tert-butylamido)(2-methylindenyl)dimethylsilanetitanium(IV)2,3-dimethyl-1,3-butadiene,

(tert-butylamido)(2-methylindenyl)dimethylsilanetitanium (I)isoprene,

(tert-butylamido)(2-methylindenyl)dimethylsilanetitanium(IV)1,3-butadiene,

(tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium (IV)2,3-dimethyl-1,3-butadiene,

(tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium(IV)isoprene

(tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanum (IV)dimethyl

(tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium(IV)dibenzyl

(tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium(IV)1,3-butadiene,

(tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium(II)1,3-pentadiene,

(tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium(II),4-diphenyl-1,3-butadiene,

(tert-butylamido)(2-methylindenyl)dimethylsilanetitanium(IV)1,3-pentadiene,

(tert-butylamido)(2-methylindenyl)dimethylsilanetitanium (IV)dimethyl,

(tert-butylamido)(2-methylindenyl)dimethylsilanetitanium (IV)dibenzyl,

(tert-butylamido)(2-methyl-4-phenylindenyl)dimethylsilanetitanium(II)1,4-diphenyl-1,3-butadiene,

(tert-butylamido)(2-methyl-4-phenylindenyl)dimethylsilanetitanium(II)1,3-pentadiene,

(tert-butylamido)(2-methyl-4-phenylindenyl)dimethylsilanetitanium(II)2,4-hexadiene,

(tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethyl-silanetitanium(IV) 1,3-butadiene,

(tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilanetitanium(IV) 2,3-dimethyl-1,3-butadiene,

(tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilanetitanium(IV) isoprene,

(tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethyl-silanetitanium(II) 1,4-dibenzyl-1,3-butadiene,

(tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilanetitanium(II) 2,4-hexadiene,

(tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethyl-silanetitanium(II) 3-methyl-1,3-pentadiene,

(tert-butylamido)(2,4-dimethylpentadien-3-yl)dimethylsilanetitaniumdimethyl,

(tert-butylamido)(6,6-dimethylcyclohexadienyl)dimethylsilanetitaniumdimethyl,

(tert-butylamido)(1,1-dimethyl-2,3,4,9,10-η-1,4,5,6,7,8-hexahydronaphthalen-4-yl)dimethylsilanetitaniumdimethyl,

(tert-butylamido)(1,1,2,3-tetramethyl-2,3,4,9,10-η-1,4,5,6,7,8-hexahydronaphthalen-4-yl)dimethylsilanetitaniumdimethyl

(tert-butylamido)(tetramethyl-η⁵-cyclopentadienylmethylphenylsilanetitanium (IV) dimethyl,

(tert-butylamido)(tetramethyl-η⁵-cyclopentadienylmethylphenylsilanetitanium (II) 1,4-diphenyl-1,3-butadiene,

1-(tert-butylamido)-2-(tetramethyl-η⁵-cyclopentadienyl)ethanediyltitanium(IV) dimethyl,

1-(tert-butylamido)-2-(tetramethyl-η⁵-cyclopentadienyl)ethanediyltitanium (II)1,4-diphenyl-1,3-butadiene,

(tert-butylamido)(3-(N-pyrrolyl)indenyl)dimethylsilanetitanium(IV)2,3-dimethyl-1,3-butadiene,

(tert-butylamido)(3-(N-pyrrolyl)indenyl)dimethylsilanetitanium(IV)isoprene

(tert-butylamido)(3-(N-pyrrolyl)indenyl)dimethylsilanetitanium(IV)dimethyl

(tert-butylamido)(3-(N-pyrrolyl)indenyl)dimethylsilanetitanium(IV)dibenzyl

(tert-butylamido)(3-(N-pyrrolyl)indenyl)dimethylsilanetitanium(IV)1,3-butadiene,

(tert-butylamido)(3-(N-pyrrolyl)indenyl)dimethylsilanetitanium(II)1,3-pentadiene,

(tert-butylamido)(3-(N-pyrrolyl)indenyl)dimethylsilanetitanium(II)1,4-diphenyl-1,3-butadiene, and

(tert-butylamido)(3-N-pyrrolidinylinden-1-yl)dimethylsilanetitanium(IV)dimethyl.

Other catalysts, especially catalysts containing other Group 4 metals,will, of course, be apparent to those skilled in the art. Most highlypreferred metal complexes for use herein are the following metalcomplexes:

(t-butylamido)dimethyl(tetramethylcyclopentadienyl)silanetitaniumdimethyl,

(t-butylamido)dimethyl(tetramethylcyclopentadienyl)silanetitanium(II)1,3-pentadiene,

(t-butylamido)dimethyl(tetramethylcyclopentadienyl)silanetitanium(II)1,4 diphenyl-1,3-butadiene,

(cyclohexylamido)dimethyl(tetramethylcyclopentadienyl)silanetitaniumdimethyl,

cyclohexylamido)dimethyl(tetramethylcyclopentadienyl)silanetitanium(II)1,3-pentadiene,

cyclohexylamido)dimethyl(tetramethylcyclopentadienyl)silanetitanium(II)1,4 diphenyl-1,3-butadiene,

(cyclododecylamido)dimethyl(tetramethylcyclopentadienyl)silanetitaniumdimethyl,

(cyclododecylamido)dimethyl(tetramethylcyclopentadienyl)silanetitanium(II)1,3-pentadiene,

(cyclododecylamido)dimethyl(tetramethylcyclopentadienyl)silanetitanium(II)1,4 diphenyl-1,3-butadiene,

(t-butylamido)dimethyl(2-methyl-s-indacen-1-yl)silanetitanium dimethyl,

(t-butylamido)dimethyl(2-methyl-s-indacen-1-yl)silanetitanium(II)1,3-pentadiene,

(t-butylamido)dimethyl(2-methyl-s-indacen-1-yl)silanetitanium (II)1,4diphenyl-1,3-butadiene,

(cyclohexylamido)dimethyl(2-methyl-s-indacen-1-yl)silanetitaniumdimethyl,

cyclohexylamido)dimethyl(2-methyl-s-indacen-1-yl)silanetitanium(II)1,3-pentadiene,

cyclohexylamido)dimethyl(2-methyl-s-indacen-1-yl)silanetitanium(II)1,4diphenyl-1,3-butadiene,

(cyclododecylamido)dimethyl(2-methyl-s-indacen-1-yl)silanetitaniumdimethyl,

(cyclododecylamido)dimethyl(2-methyl-s-indacen-1-yl)silanetitanium(II)1,3-pentadiene,

(cyclododecylamido)dimethyl(2-methyl-s-indacen-1-yl)silanetitanium(II)1,4diphenyl-1,3-butadiene,

(t-butylamido)dimethyl(3,4-(cyclopenta(l)phenanthren-1-yl)silanetitaniumdimethyl,

(t-butylamido)dimethyl(3,4-(cyclopenta(l)phenanthren-1-yl)silanetitanium(II)1,3-pentadiene,

(t-butylamido)dimethyl(3,4-(cyclopenta(l)penanthren-1-yl)silanetitanium(II)1,4diphenyl-1,3-butadiene,

(cyclohexylamido)dimethyl(3,4-(cyclopenta(l)phenanthren-1-yl)silanetitaniumdimethyl,

cyclohexylamido)dimethyl(3,4-(cyclopenta(l)phenanthren-1-yl)silanetitanium(II)1,3-pentadiene,

cyclohexylamido)dimethyl(3,4-(cyclopenta(l)phenanthren1-yl)silanetitanium(II)1,4 diphenyl-1,3-butadiene,

(cyclododecylamido)dimethyl(3,4-(cyclopenta(l)phenanthren-1-yl)silanetitaniumdimethyl,

(cyclododecylamido)dimethyl(3,4-(cyclopenta(l)phenanthren-1-yl)silanetitanium(II)1,3-pentadiene,

(cyclododecylamido)dimethyl(3,4-(cyclopenta(l)phenanthren-1-yl)silanetitanium(II)1,4diphenyl-1,3-butadiene,

(t-butylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitaniumdimethyl,

(t-butylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitanium(II)1,3-pentadiene,

(t-butylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitanium(II)1,4diphenyl-1,3-butadiene,

(cyclohexylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitaniumdimethyl,

cyclohexylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitanium(II)1,3-pentadiene,

cyclohexylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitanium(II)1,4diphenyl-1,3-butadiene,

(cyclododecylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitaniumdimethyl,

(cyclododecylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitanium(II)1,3-pentadiene,

(cyclododecylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitanium(II)1,4diphenyl-1,3-butadiene,

(t-butylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitaniumdimethyl,

(t-butylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitanium(II)1,3-pentadiene,

(t-butylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitanium(II)1,4 diphenyl-1,3-butadiene,

(cyclohexylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitaniumdimethyl,

cyclohexylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitanium(II)1,3-pentadiene,

cyclohexylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitanium(II)1,4dipheney-1,3-butadiene,

(cyclododecylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitaniumdimethyl,

(cyclododecylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitanium(II)1,3-pentadiene,

(cyclododecylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitanium(II)1,4diphenyl-1,3-butadiene,

(t-butylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetitaniumdimethyl,

(t-butylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetitanium(II)1,3-pentadiene,

(t-butylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetitanium(II)1,4diphenyl-1,3-butadiene,

(cyclohexylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetitaniumdimethyl,

cyclohexylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetitanium(II)1,3-pentadiene,

cyclohexylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetitanium(II)1,4diphenyl-1,3-butadiene,

(cyclododecylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetitaniumdimethyl,

(cyclododecylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetitanium(II)1,3-pentadiene,

(cyclododecylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetitanium(II)1,4diphenyl-1,3-butadiene,

(t-butylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetitaniumdimethyl,

(t-butylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetitanium(II)1,3-pentadiene,

(t-butylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetitanium(II)1,4 diphenyl-1,3-butadiene,

(cyclohexylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetitaniumdimethyl,

cyclohexylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetitanium(II)1,3-pentadiene,

cyclohexylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetitanium(II)1,4diphenyl-1,3-butadiene,

(cyclododecylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetitaniumdimethyl,

(cyclododecylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetitanium(II)1,3-pentadiene,

(cyclododecylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetitanium(II)1,4diphenyl-1,3-butadiene,

1,2-ethanebis(inden-1-yl)zirconium dimethyl,

1,2-ethanebis(inden-1-yl)zirconium(II)1,3-pentadiene,

1,2-ethanebis(inden-1-yl)zirconium(II)1,4 diphenyl-1,3-butadiene,

1,2-ethanebis(2-methyl-4-phenylinden-1-yl)zirconium dimethyl,

1,2-ethanebis(2-methyl-4-phenylinden-1-yl)zirconium(II)1,3-pentadiene,

1,2-ethanebis(2-methyl-4-phenylinden-1-yl)zirconium(II)1,4diphenyl-1,3-butadiene, dimethylsilanebis(inden-1-yl)zirconium dimethyl,

dimethylsilanebis(inden-1-yl)zirconium(II)1,3-pentadiene,

dimethylsilanebis(inden-1-yl)zirconium(II)1,4 diphenyl-1,3-butadiene,

dimethylsilanebis(2-methyl-4-phenylinden-1-yl)zirconium dimethyl,

dimethylsilanebis(2-methyl-4-phenylinden-1-yl)zirconium(II)1,3-pentadiene,and

dimethylsilanebis(2-methyl-4-phenylinden-1-yl)zirconium(II 1,4diphenyl-1,3-butadiene.

The cocatalysts of the invention may be, and preferably are used incombination with an oligomeric or polymeric alumoxane compound, atri(hydrocarbyl)aluminum compound, adi(hydrocarbyl)(hydrocarbyloxy)aluminum compound, adi(hydrocarbyl)(dihydrocarbyl-amido)aluminum compound, abis(dihydrocarbyl-amido)(hydrocarbyl)aluminum compound, adi(hydrocarbyl)amido(disilyl)aluminum compound, adi(hydrocarbyl)-amido(hydrocarbyl)(silyl)aluminum compound, abis(dihydrocarbylamido)(silyl)aluminum compound, or a mixture of theforegoing compounds, having from 1 to 20 non-hydrogen atoms in eachhydrocarbyl, hydrocarbyloxy, or silyl group, if desired. These aluminumcompounds are usefully employed for their beneficial ability to scavengeimpurities such as oxygen, water, and aldehydes from the polymerizationmixture as well as to react with the hydroxyl group or quiescentreactive functionality of the compounds or the reactive derivativesthereof.

Preferred aluminum compounds include C₁₋₂₀ trialkyl aluminum compounds,especially those wherein the alkyl groups are ethyl, propyl, isopropyl,n-butyl, isobutyl, pentyl, neopentyl, or isopentyl,dialkyl(aryloxy)aluminum compounds containing from 1-6 carbons in thealkyl group and from 6 to 18 carbons in the aryl group (especially(3,5-di(t-butyl)-4-methlphenoxy) diisobutylaluminum), methylalumoxane,modified methalumoxane, especially isobutyl modified alumoxane, andtri(ethylaluminum)-, tris(pentafluorophenyl)borane-, ortris(pentafluorophenyl)aluminum-modified alumoxanes or supportedderivatives thereof. (The latter compositions are previously known,having been disclosed in WO99/15534. Additional species include mixturesof aluminum containing Lewis acids as disclosed in U.S. Pat. No.6,214,760 and U.S. Pat. No. 6,211,111. The molar ratio of activator toaluminum compound is preferably from 1:10,000 to 1000:1, more preferablyfrom 1:5000 to 100:1, most preferably from 1:100 to 100:1.

The equivalent ratio of catalyst/cocatalyst (calculated based onquantity of metal in the catalyst and anionic charges on the cocatalystemployed preferably ranges from 1:10 to 10:1, more preferably from 1:5to 2:1, most preferably from 1:4 to 1:1. Mixtures of the activatingcocatalysts of the present invention may also be employed if desired.

Suitable addition polymerizable monomers include ethylenicallyunsaturated monomers, acetylenic compounds, conjugated or non-conjugateddienes, and polyenes. Preferred monomers include olefins, for examplesalpha-olefins having from 2 to 20,000, preferably from 2 to 20, morepreferably from 2 to 8 carbon atoms and combinations of two or more ofsuch alpha-olefins. Particularly suitable alpha-olefins include, forexample, ethylene, propylene, 1-butene, 1-pentene,4-methylpentene-1,1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene,1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, orcombinations thereof, as well as long chain vinyl terminated oligomericor polymeric reaction products formed during the polymerization, andC₁₀₋₃₀ α-olefins specifically added to the reaction mixture in order toproduce relatively long chain branches in the resulting polymers.Preferably, the alpha-olefins are ethylene, propene, 1-butene,4-methyl-pentene-1,1-hexene, 1-octene, and combinations of ethyleneand/or propene with one or more of such other alpha-olefins. Otherpreferred monomers include styrene, halo- or alkyl substituted styrenes,vinylbenzocyclobutene, 1,4-hexadiene, dicyclopentadiene, ethylidenenorbomene, and 1,7-octadiene. Mixtures of the above-mentioned monomersmay also be employed.

In general, the polymerization may be accomplished at conditions wellknown in the prior art for Ziegler-Natta or Kaminsky-Sinn typepolymerization reactions. Suspension, solution, slurry, gas phase orhigh pressure, whether employed in batch or continuous form or otherprocess conditions, may be employed if desired. Examples of such wellknown polymerization processes are depicted in WO 88/02009, U.S. Pat.Nos. 5,084,534, 5,405,922, 4,588,790, 5,032,652, 4,543,399, 4,564,647,4,522,987, and elsewhere. Preferred polymerization temperatures are from0-250° C. Preferred polymerization pressures are from atmospheric to3000 atmospheres.

Suitable processing conditions include solution polymerization, morepreferably continuous solution polymerization processes, conducted inthe presence of an aliphatic or alicyclic liquid diluent, preferablyusing the unsupported, quiescent reactive functionality containingcompounds. By the term “continuous polymerization” is meant that atleast the products of the polymerization are continuously removed fromthe reaction mixture, such as for example by devolatilization of aportion of the reaction mixture. Preferably one or more reactants arealso continuously added to the polymerization mixture during thepolymerization. Examples of suitable aliphatic or alicyclic liquiddiluents include straight and branched-chain C₄₋₁₂ hydrocarbons andmixtures thereof; alicyclic hydrocarbons such as cyclohexane,cycloheptane, methylcyclohexane, methylcycloheptane, and mixturesthereof, and perfluorinated hydrocarbons such as perfluorinated C₄₋₁₀alkanes, and the like. Suitable diluents also include aromatichydrocarbons (particularly for use with aromatic a-olefins such asstyrene or ring alkyl-substituted styrenes) including toluene,ethylbenzene or xylene, as well as liquid olefins (which may act asmonomers or comonomers) including ethylene, propylene, butadiene,cyclopentene, 1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene,1,4-hexadiene, 1-octene, 1-decene, styrene, divinylbenzene,allylbenzene, vinyltoluene (including all isomers alone or inadmixture), and the like. Mixtures of the foregoing are also suitable.The foregoing diluents may also be advantageously employed during thesynthesis of the metal complexes and catalyst activators of the presentinvention.

In most polymerization reactions the molar ratio ofcatalyst:polymerizable compounds employed is from 10⁻¹²:1 to 0.1:1, morepreferably from 10⁻¹²:1 to 10⁻⁵:1.

The catalyst composition of the invention may also be utilized incombination with at least one additional homogeneous or heterogeneouspolymerization catalyst in the same reactor or in separate reactorsconnected in series or in parallel to prepare polymer blends havingdesirable properties.

Molecular weight control agents can be used in combination with thepresent cocatalysts. Examples of such molecular weight control agentsinclude hydrogen, trialkyl aluminum compounds or other known chaintransfer agents. A particular benefit of the use of the presentcocatalysts is the ability (depending on reaction conditions) to producenarrow molecular weight distribution cc-olefin homopolymers andcopolymers in greatly improved catalyst efficiencies. Preferred polymershave Mw/Mn of less than 2.5, more preferably less than 2.3. Such narrowmolecular weight distribution polymer products are highly desirable dueto improved tensile strength properties.

The catalyst composition of the present invention can also be employedto advantage in the gas phase polymerization and copolymerization ofolefins. Gas phase processes for the polymerization of olefins,especially the homopolymerization and copolymerization of ethylene andpropylene, and the copolymerization of ethylene with higher alphaolefins such as, for example, 1-butene, 1-hexene, 4-methyl-1-pentene arewell known in the art. Such processes are used commercially on a largescale for the manufacture of high density polyethylene (HDPE), mediumdensity polyethylene (MDPE), linear low density polyethylene (LLDPE) andpolypropylene.

The gas phase process employed can be, for example, of the type whichemploys a mechanically stirred bed or a gas fluidized bed as thepolymerization reaction zone. Preferred is the process wherein thepolymerization reaction is carried out in a vertical cylindricalpolymerization reactor containing a fluidized bed of polymer particlessupported above a perforated plate, the fluidisation grid, by a flow offluidisation gas.

The gas employed to fluidize the bed comprises the monomer or monomersto be polymerized, and also serves as a heat exchange medium to removethe heat of reaction from the bed. The hot gases emerge from the top ofthe reactor, normally via a tranquilization zone, also known as avelocity reduction zone, having a wider diameter than the fluidized bedand wherein fine particles entrained in the gas stream have anopportunity to gravitate back into the bed. It can also be advantageousto use a cyclone to remove ultra-fine particles from the hot gas stream.The gas is then normally recycled to the bed by means of a blower orcompressor and one or more heat exchangers to strip the gas of the heatof polymerization.

A preferred method of cooling of the bed, in addition to the coolingprovided by the cooled recycle gas, is to feed a volatile liquid to thebed to provide an evaporative cooling effect. The volatile liquidemployed in this case can be, for example, a volatile inert liquid, forexample, a saturated hydrocarbon having 3 to 8, preferably 4 to 6,carbon atoms. In the case that the monomer or comonomer itself is avolatile liquid, or can be condensed to provide such a liquid this canbe suitably be fed to the bed to provide an evaporative cooling effect.Examples of olefin monomers which can be employed in this manner areolefins containing from 3 to 8, preferably from 3 to 6 carbon atoms. Thevolatile liquid evaporates in the hot fluidized bed to form gas whichmixes with the fluidizing gas. If the volatile liquid is a monomer orcomonomer, it will undergo some polymerization in the bed. Theevaporated liquid then emerges from the reactor as part of the hotrecycle gas, and enters the compression/heat exchange part of therecycle loop. The recycle gas is cooled in the heat exchanger and, ifthe temperature to which the gas is cooled is below the dew point,liquid will precipitate from the gas. This liquid is desirably recycledcontinuously to the fluidized bed. It is possible to recycle theprecipitated liquid to the bed as liquid droplets carried in the recyclegas stream, as described, for example, in EP-A-89691, U.S. Pat. No.4,543,399, WO 94/25495 and U.S. Pat. No. 5,352,749. A particularlypreferred method of recycling the liquid to the bed is to separate theliquid from the recycle gas stream and to reinject this liquid directlyinto the bed, preferably using a method which generates fine droplets ofthe liquid within the bed.

The polymerization reaction occurring in the gas fluidized bed iscatalyzed by the continuous or semi-continuous addition of catalyst.Such catalyst can be supported on an inorganic or organic supportmaterial if desired. Direct addition of the catalyst in the form of asolution in a solvent to a gas-phase polymerization reactor may beemployed as well. The catalyst can also be subjected to aprepolymerization step, for example, by polymerizing a small quantity ofolefin monomer in a liquid inert diluent, to provide a catalystcomposite comprising catalyst particles embedded in olefin polymerparticles.

The polymer is produced directly in the fluidized bed by catalyzed(co)polymerization of the monomer(s) on the fluidized particles ofcatalyst, supported catalyst or prepolymer within the bed. Start-up ofthe polymerization reaction is achieved using a bed of preformed polymerparticles, which, preferably, is similar to the target polyolefin, andconditioning the bed by drying with inert gas or nitrogen prior tointroducing the catalyst, the monomer(s) and any other gases which it isdesired to have in the recycle gas stream, such as a diluent gas,hydrogen chain transfer agent, or an inert condensable gas whenoperating in gas phase condensing mode. The produced polymer isdischarged continuously or discontinuously from the fluidized bed asdesired, optionally exposed to a catalyst kill and optionallypelletized.

Slurry polymerization conditions and supported catalyst preparationtechniques for use therein are well known from the published literature.Generally such catalysts are prepared by the same techniques as areemployed for making supported catalysts used in gas phasepolymerizations. Slurry polymerization conditions generally encompasspolymerization of a C₂₋₂₀ olefin, diolefin, cycloolefin, or mixturethereof in an aliphatic solvent at a temperature below that at which thepolymer is readily soluble in the presence of a supported catalyst.Slurry phase processes particularly suited for the polymerization ofC₂₋₆ olefins, especially the homopolymerization and copolymerization ofethylene and propylene, and the copolymerization of ethylene with C₃₋₈α-olefins such as, for example, 1-butene, 1-hexene, 4-methyl-1-penteneand 1-octene are well known in the art. Such processes are usedcommercially on a large scale for the manufacture of high densitypolyethylene (HDPE), medium density polyethylene (MDPE), linear lowdensity polyethylene (LLDPE) and polypropylene, especially isotacticpolypropylene.

In addition to the foregoing techniques for coordination additionpolymerizations, the present compounds and compositions disclosed hereinare useful as initiators or catalysts in the field of cationicpolymerization. Preferred monomers for such cationic polymerizationsinclude styrene, α-methylstyrene, ring alkyl-substituted styrene,isobutylene, and mixtures thereof. Preferred temperatures for cationicpolymerizations are from −100 to 50° C., preferably −80 to 20° C.

EXAMPLES

It is understood that the present invention is operable in the absenceof any component which has not been specifically disclosed. Thefollowing examples are provided in order to further illustrate theinvention and are not to be construed as limiting. Unless stated to thecontrary, all parts and percentages are expressed on a weight basis. Theterm “overnight”, if used, refers to a time of approximately 16-18hours, “room temperature”, if used, refers to a temperature of 20-25°C., and “mixed alkanes” refers to a mixture of mostly C₆-C₁₂ alkanesavailable commercially under the trademark Isopar E™ from ExxonChemicals Inc.

All manipulation of air sensitive materials was performed in an argonfilled, vacuum atmospheres, glove box or on a high vacuum line usingstandard Shlenk techniques. Toluene was purified by passage throughcolumns packed with activated alumina (Kaiser A-2) and supported copper(Engelhard, Cu-0224 S). Hexanes were purified by distillation fromsodium benzophenone ketyl. Tris(pentafluorophenyl)borane (FAB) waspurchased from Boulder Scientific. Dioctadecylmethylamine is abis(hydrogenated tallow) alkylamine of approximate formulation(C₁₈H₃₅)₂CH₃N, available commercially under the tradename Armeen™ M2HTfrom Akzo Nobel, Inc., and was used as received.

Example 1 [H(C₁₄₋₁₈H₂₇₋₃₅)₂(CH₃)N]⁺{(C₁₇H₃₃C(O)O)[B(C₆F₅)₃]₂}⁻

A) Synthesis of [H(C₁₄₋₁₈H₂₇₋₃₅)₂(CH₃)N]⁺[(C₁₇H₃₃C(O)O]⁻

To a flask containing 533 mg (1.87 mmol) of stearic acid 1000 mg (1.87mmol) of Armeen™ M2HT and 25 g of hexane were added. The reactionmixture was warmed until a clear solution resulted. After 30 minutes ofstirring the volatiles were removed under vacuum, leaving the desiredproduct as a white solid.

B) Synthesis of [H(C₁₄₋₁₈H₂₇₋₃₅)₂(CH₃)N]⁺{(C₁₇H₃₃C(O)O)[B(C6F₅) ₃]₂}⁻

A flask containing FAB (123 mg, 0.24 mmol) and 20 ml of toluene wascharged with 99 mg (0.12 mmol) of the ammonium stearate salt prepared instep A). A clear, 0.006 molar solution of the desired complex for use inpolymerization resulted.

Example 2

The reaction conditions of Example 1 were substantially repeated,excepting that the ammonium stearate salt was not isolated beforeaddition of 2 equivalents of FAB. A clear, toluene solution of thedesired product resulted. Example 3

[H(C₁₄₋₁₈H₂₇₋₃₅)₂(CH₃)N]⁺{NO₃[B(C₆F₅)₃]₂}⁻

A) Synthesis of [H(C₁₄₋₁₈H₂₇₋₃₅)₂(CH₃)N]⁺[NO₃]⁻

To a flask containing 277 mg of silver nitrate suspended in 35 g hexane,932 mg of the hydrochloride salt of Armeen™ M2HT were added. The mixturewas heated to 40° C. for 15 minutes, cooled to room temperature andsonicated for 2 hours, then stirred an additional 48 hours. The reactionmixture was warmed again to 40° C. and filtered through a pad ofdiatomaceous earth. The filtrate containing the desired product wasretained.

B) Synthesis of [H(C₁₄₋₁₈H₂₇₋₃₅)₂(CH₃)N]⁺{(NO₃)[B(C₆F₅)₃]₂ }−

FAB (2.5 g, 4.8 mmol) was added to the filtrate obtained from step A).After 1 hour, all volatiles were removed under reduced pressure. Theresulting product was redissolved in toluene to give a clear, 0.006 Msolution of the desired product for use in polymerization.

Example 4 [H(C₁₄₋₁₈H₂₇₋₃₅)₂(CH₃)N]⁺{C(C(O)CH₃)₃[B(C₆F₅)₃]₃}−

Methyl triacetyl (HC(C(O)CH₃)₃, 17 mg, 0.13 mmoles) and Armeen™ M2HT((C₁₄₋₁₈H₂₇₋₃₅) ₂(CH₃)N, 64 mg, 0.13 mmoles) were combined in 10 ml oftoluene. After 15 minutes, FAB, (6.082 g of a 3.03 weight percentsolution in mixed alkanes, 0.36 mmole) was added. After 10 minutesstirring another 1.0 ml of toluene was added to give a 0.006 molarsolution which was used as a polymerization catalyst solution withoutfurther modification.

Example 5 [H(C₁₄₋₁₈H₂₇₋₃₅)₂(CH₃)N]⁺{C₉O₂H₅[B(C₆F₅)₃]₂}−

Indan-1,3-dione (C₉O₂H₆, 17 mg, 0.12 mmoles) and Armeen™ M2HT((C₁₄₋₁₈H₂₇₋₃₅) ₂(CH₃)N, 64 mg, 0.13 mmoles) were combined in 10 ml oftoluene. After 15 minutes, FAB, (4.055 g of a 3.03 weight percentsolution in mixed alkanes, 0.24 mmole) was added. After 10 minutesstirring another 4.2 ml of toluene was added to give a 0.006 molarsolution which was used as a polymerization catalyst solution withoutfurther modification.

Polymerizations

Mixed alkanes and liquid olefins are purified by sparging with purifiednitrogen followed by passage through columns containing alumina (A-2,available from LaRoche Inc.) and Q5 reactant (available from EnglehardChemicals Inc.) at 50 psig (450 kPa) using a purified nitrogen pad. Alltransfers of solvents and solutions described below are accomplishedusing a gaseous pad of dry, purified nitrogen or argon. Gaseous feeds tothe reactor are purified by passage through columns of A-204 alumina(available from LaRoche Inc.) and Q5 reactant. The aluminas arepreviously activated by treatment at 375° C. with nitrogen, and Q5reactant is activated by treatment at 200° C. with 5 percent hydrogen innitrogen.

A stirred, two-liter Parr reactor was charged with approximately 433 gof toluene and 455 g of 1-octene comonomer. Hydrogen was added as amolecular weight control agent by differential pressure expansion from a75 mL addition tank at 50 psig (450 kPa). The reactor was heated to 90°C. and saturated with ethylene at 200 psig (1.4 MPa). The appropriateamount of catalyst,tetramethylcyclopentadienyl)dimethyl(t-butylamido)silane titanium (II)1,3-pentadiene and cocatalyst (either an example of the invention or acomparative cocatalyst, dioctadecylmethylammoniumtetrakis(pentafluorophenyl)borate, DAB) in toluene were premixed in aglovebox in a 1:1.1 molar ratio and transferred to a catalyst additiontank and injected into the reactor. (Periodic additions ofcatalyst/cocatalyst solution may be added during the course of the run.)The polymerization conditions were maintained during the run withethylene on demand.

The resulting solution was removed from the reactor into a nitrogenpurged collection vessel containing 100 ml of isopropyl alcohol and 20ml of a 10 weight percent toluene solution of hindered phenolantioxidant (Irganox™ 1010 from Ciba Geigy Corporation) and phosphorusstabilizer (Irgafos™ 168 from Ciba Geigy Corporation). Polymers formedare dried in a programmed vacuum oven with a maximum temperature of 140°C. and a 20 hour heating period. Results of the polymerization arereported in Table 1.

TABLE 1 Run Cocatalyst Max C₂H₄ flow (g/min) Efficiency²  1* DAB¹ 31.81.8  2* ″ 31.8 1.8  3 Ex. 1 39.3 2.7  4 ″ 31.8 2.4  5* DAB 24.9 1.8  6*″ 27.8 —  7 Ex. 3 30.7 —  8 ″ 19.2 —  9* DAB 24.7 — 10* ″ 14.8 1.5 11Ex. 4 23.7 1.6 12 ″ 26.2 1.7 13 Ex. 5 30.6 2.0 14 ″ 30.1 2.0 15* DAB13.4 1.3 *comparative, not an example of the invention¹dioctadecylmethylammonium tetrakis(pentafluorophenyl)borate²efficiency, g polymer/μg Ti

What is claimed is:
 1. A polymerization process comprising contactingone or more α-olefins under polymerization conditions with a catalystcomposition comprising the combination or reaction product resultingfrom combining, 1) a Group 3-10 or Lanthanide metal complex. 2) acompound corresponding to the formula: (A*^(+a))_(b)(Z*J*_(j))^(−c)_(d), wherein: A* is a proton or a cation of from 1 to 80 atoms, notcounting hydrogen atoms, said A* having a charge+a; Z* is an anion groupof from 1 to 50 atoms, not counting hydrogen atoms, further containingtwo or more Lewis base sites, said Z* being the conjugate base of aninorganic Bronsted acid or a carbonyl- or non-cyclic, imino-groupcontaining organic Bronsted acid; J* independently each occurrence is aLewis acid of from 1 to 80 atoms, not counting hydrogen atoms,coordinated to at least one Lewis base site of Z*, and optionally two ormore such J* groups may be joined together in a moiety having multipleLewis acidic functionality; j is a number from 1 to 12; and a, b, c, andd are integers from 1 to 3, with the proviso that a×b is equal to c×d;3) optionally an organoaluminum compound, and 4) further optionally, asolid, particulated support.
 2. A polymerization process according toclaim 1 that is a solution polymerization.
 3. A polymerization processaccording to claim 1 that is a gas phase polymerization.
 4. Apolymerization process according to claim 1 that is a slurrypolymerization.
 5. A polymerization process according to claim 1 that isa cationic polymerization.
 6. A process according to claim 1 if whereinZ* is selected from the group consisting of: NO₃ ⁻, PO₄ ³⁻.SO₄ ²⁻, RSO₃⁻, CO₃ ²⁻, [RC(O)O]⁻, [RC(NR)NR]⁻, [R′C(O)CR′C(O)R′]⁻, [(R′C(O))₃C]⁻,[RC(NR)CRC(NR)R]⁻, and [(RC(NR))₃C]⁻, wherein each R is independently ahydrogen-; hydrocarbyl-; or halocarbyl-group; a hydrocarbyl groupfurther substituted with one or more carbonyl-, halo-, hydroxy-,dialkylamino-, dialkylaluminumoxy-, trihydrocarbylsilyl-,trihydrocarbylsiloxy-, or hydrocarbyloxy-groups; or a halocarbyl groupfurther substituted with one or more carbonyl-, hydroxy-, dialkylamino-,dialkylaluminumoxy-, trihydrocarbylsilyl-, trihydrocarbylsiloxy-, orhydrocarbyloxy-groups; and each R′ is independently R or two R′ groupsmay be joined together thereby forming a divalent group.
 7. A processaccording to claim 1 wherein Z* is an acetylacetonate,cyclohexa-1,3-dionate, [RC(O)O]⁻ or NO₃ ⁻², wherein R is a C₆₋₂₄hydrocarbyl group, most preferably a C₁₂₋₂₄ alkyl group, or anindane-1,3-dione anion or methyl triacetyl anion of the followingstructure:


8. A process according to claim 1 wherein A*^(+a) is a proton or isselected from the group consisting of ammonium, sulfonium, phosphonium,oxonium, carbonium, silylium, ferrocenium, Ag⁺, and Pb⁺² cations.
 9. Aprocess according to claim 1, wherein A*^(+a) is a trimethylammonium-,triethylammonium-, tripropylammonium-, tri(n-butyl) ammonium-,methyldi(C₁₄₋₁₈ alkyl)ammonium-, dimethyl(C₁₄₋₁₈ alkyl)ammonium-,N,N-dimethylanilinium-, N,N-diethylanilinium-,N,N-dimethyl(2,4,6-trimethylanilinium)-, N,N-di(tetradecyl)lanilinium-,N,N-di(tetradecyl) (2,4,6-trimethylanilinium)-,N,N-di(octadecyl)lanilinium-,N,N-di(octadecyl)-2,4,6-trimethylanilinium)-, ormethyldicyclohexylammonium-cation.
 10. A process according to claim 1wherein J*′ is tris(pentafluorophenyl)borane ortris(pentafluorophenyl)alumane).
 11. A process according to claim 1wherein compound 2) is a bis(tris(pentafluorophenyl)borane)-coordinatedderivative of a trihydrocarbylammonium stearate or amono(tris(pentafluorophenyl)-borane)-coordinated derivative of atrihydrocarbylammonium stearate.
 12. A process according to claim 1wherein an organoaluminum compound is included in the catalystcomposition.
 13. A process according to claim 13 wherein theorganoaluminum compound is an alumoxane.
 14. A process according toclaim 14 wherein a solid, particulated support is present.
 15. A processaccording to claim 1 wherein component 1) is a Group 4 metal complex.